Method for producing a semiconductor device including doping with a catalyst that is a group IV element

ABSTRACT

A silicon film provided on a blocking film 102 on a substrate 101 is made amorphous by doping Si+, and in a heat-annealing process, crystallization is started in parallel to a substrate from an an 100 where lead serving as a crystallization-promoting catalyst is introduced.

This application is a Division of application Ser. No. 08/715,770, filedSep. 19, 1996 now U.S. Pat. No. 5,830,784; which itself is Continuationof application Ser. No. 08/248,085, filed May 24, 1994, now abandoned.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to a semiconductor device having TFTs (thin filmtransistors) provided on an insulating substrate of glass or the like,and a method for producing the semiconductor device.

2. Description of Related Art

TFTs have been conventionally formed on a glass substrate to form asemiconductor device such as an active matrix liquid crystal device oran image sensor. The TFTs are used, for example, to drive the pixels ofthe liquid crystal device.

The TFTs used in the above devices are generally formed of a siliconsemiconductor layer in the form of a thin film. The siliconsemiconductor of a thin-film type is classified into two types, anamorphous silicon semiconductor (a-Si) type and a crystalline siliconsemiconductor type. The amorphous silicon semiconductor can berelatively easily produced at a low film-forming temperature by avapor-phase deposition method. Therefore, this type is suitable for massproduction, and it has been most generally used. However, this type ofsilicon semiconductor has inferior physical properties such aselectrical conductivity, etc. to the crystalline silicon semiconductor.Therefore, in order to more improve a high-speed response characteristicof TFTs, a producing method for TFTs comprising crystalline siliconsemiconductor has been strongly required to be established. As thesilicon semiconductor having crystallinity have been knownpolycrystalline silicon, microcrystalline silicon, amorphous siliconcontaining crystal components, semi-amorphous silicon having anintermediate state between crystallinity and amorphousness, etc.

As a method for obtaining a crystalline semiconductor layer, it is wellknown that an amorphous silicon is initially deposited on a substrateand then heated at a high temperature.

However, this method requires a heating temperature above 600° C., andthus an inexpensive glass substrate is not usable. Therefore, it isrequired to establish an improved method which enables the heatcrystallization at a lower temperature. Particularly in case of presentliquid crystal display devices, a large-area screen design is beingpromoted, and thus use of a large-size glass substrate is required. Whena large-size glass substrate is used, contraction and distortion of asubstrate occur in the heating process which is indispensable to producecrystalline semiconductors, and they cause a critical problem that theprecision of a masking process is reduced. Particularly in a case of7059 glass which is most generally used at present, it has a distortionpoint of 593° C., and it is greatly deformed in a conventional heatcrystallization method. In addition to the heat problem as describedabove, a heating time required for crystallization is over several tenshours in a present process, and thus the heating time must be shortened.

SUMMARY OF THE INVENTION

An object of the present invention is to provide a method capable ofsolving the above problems, and specifically to provide a process forproducing a silicon semiconductor thin film having crystallinityutilizing a method of heating an amorphous silicon thin film tocrystallize the thin film, in which both of lowering of the temperaturefor crystallization and shortage of the heating time for crystallizationcan be performed. A silicon semiconductor having crystallinity which ismanufactured using the process according to this invention has the samephysical properties as or physical properties superior to thatmanufactured by a conventional technique, and it is usable in an activelayer area of TFTs.

The inventors of this application have made the following experimentsand consideration for a method of forming an amorphous siliconsemiconductor film as described above by a CVD method or a sputteringmethod, and then heating the film to crystalize the film.

An amorphous silicon film is initially formed on a glass substrate, andthen the film is crystallized by heating. The inventors investigated themechanism of this crystallization. Through the experiments, it wasobserve that crystal growth of silicon starts at an interface betweenthe glass substrate and the amorphous silicon and proceeds vertically tothe substrate surface into a pillar shape in the case that the thicknessof the film is larger than a certain thickness.

The above phenomenon is considered as progressing on the basis of amechanism that crystalline nuclei serving as geneses for crystal growth(species serving as geneses for crystal growth) exist between the glasssubstrate and the amorphous silicon film, and the crystal grows from thecrystalline nuclei. These crystalline nuclei are considered as beingimpurity metal elements or crystal components (as is called as acrystallized glass, it is considered that crystal components of siliconoxide exist on the surface of the glass substrate) existing on thesurface of the substrate in a very small amount.

Accordingly, it is expected that a crystallization temperature can belowered by introducing crystal nuclei more positively. In order toconfirm an effect of introducing crystal nuclei, the followingexperiment was tried. That is, a thin film of different metal in a verysmall amount was beforehand formed on a substrate, then an amorphoussilicon thin film was formed on the different metal film, and thenheat-crystallization was conducted on the amorphous silicon thin film.As a result, it was proved that the crystallization temperature waslowered when thin films of some different kinds of metal were beforehandformed on the substrate, and it was expected that crystal growth usingforeigners as crystal nuclei had conducted. Accordingly, a more detailedmechanism for plural kinds of impurity metal which could lower thecrystallization temperature was studied.

The crystallization mechanism can be considered to be classified intotwo stages which are an initial nucleus generation stage and asubsequent crystal growth stage from the nuclei. The speed of theinitial nucleus generation can be detected by measuring measuring a timeelapsing until spotted fine crystals occur at a constant temperature.This time could be shortened in all cases where the thin films of theabove kinds of impurity metal were formed on the substrate, and theeffect of the introduction of the crystal nuclei on the lowering of thecrystallization temperature can be proved. As an unexpected result,through an experiment for examining variation of growth of crystalgrains with variation of the heating time after generation of crystalnuclei, it was observed that the speed of the crystal growth after thegeneration of the nuclei was also rapidly increased when a thin film ofa certain kind of metal was formed on a substrate, an amorphous siliconthin film was formed on the metal thin film and then the amorphoussilicon thin film was crystallized. A mechanism for this effect has notyet been elucidated at present, however, it is guessed that anycatalytic effect acts.

At any rate, it was proved that when a thin film was formed of a certainkind metal in a very small amount, an amorphous silicon thin film wasformed on the metal thin film and then the amorphous silicon thin filmwas crystallized by heating, sufficient crystallinity which had not beenexpected in the prior art could be obtained at a temperature below 580°C. and for about 4 hours due to the two effects as described above. Lead(Pd) is the best material which is experimentally proved as providingthe most remarkable effect in all impurity metals having such an effect.In addition to lead, the other group IV elements such as Sn has beenfound suitable for promoting the crystallization.

The following is an example showing an effect of formation of a leadthin film. In a case where an amorphous silicon thin film was formed bya plasma CVD method on a substrate (coring 7059 glass) which had beensubjected to no treatment, that is, on which no lead thin film had beenformed, and then heated under a nitrogen atmosphere to crystallize theamorphous silicon thin film, a heating time over ten hours was requiredfor a heating temperature of 600° C. On the other hand, in a case wherean amorphous silicon thin film was formed on a substrate on which a leadthin film in a very small amount (hereinafter referred to as a tracelead thin film) had been formed, the same crystal state as the formercase could be obtained by heating the amorphous silicon thin film forabout 4 hours. The crystallization of the amorphous silicon thin filmwas judged using a Raman spectrum in this experiment. From thisexperiment, it is apparent that lead has a large effect.

As is apparent from the foregoing, formation of an amorphous siliconthin film after a trace lead thin film is formed enables the lowering ofthe crystallization temperature and the shortening of thecrystallization time. This process will be described in more detail onthe assumption that this process is applied to a TFT producing process.As described later, the same effect can be obtained by forming a leadthin film on not only a substrate, but also on an amorphous silicon thinfilm, or by implanting the lead into the amorphous silicon by an ionimplantation method. Accordingly, these treatments are commonly referredto as "trace lead addition" in the specification of this application.

First, a method for the trace lead addition will be described.

It has been known that the trace lead addition can provide the sameeffect on the lowering of the crystallization temperature in both caseswhere a trace lead thin film is formed on a substrate and then anamorphous silicon thin film is formed on the trace lead thin film, andwhere an amorphous silicon film is formed and then a trace lead thinfilm is formed on the amorphous silicon film, and any film-formingmethod such as a sputtering method, a deposition method, spin coating,coating or the like may be used as a film-forming method. However, inthe method of forming the trace lead thin film on the substrate, theeffect becomes more remarkable by forming a silicon oxide film on a 7059glass substrate and then forming the trace lead thin film on the siliconoxide film than by directly forming the trace lead thin film on thesubstrate. As one of reasons for this fact, it would be considered thatdirect contact between silicon and lead is important for thelow-temperature crystallization, and components other than siliconserves to obstruct direct contact or reaction between silicon and leadin the case of using a 7059 glass substrate.

It was proved that the substantially same effect could be obtained byadding lead with the ion implantation method as well as the method offorming the trace lead thin film in contact with the lower surface orupper surface of the amorphous silicon thin film as described above. Thelowering of the crystallization temperature was observed for addition oflead of 1×10¹⁵ atoms/cm³ or more. However, it was observed that foraddition of lead of 1×10²¹ atoms/cm³ or more, the shape of the peak of aRaman spectrogram was clearly different from that of silicon itself, sothat a practically usable range of lead addition is from 1×10¹⁵atoms/cm³ to 5×10¹⁹ atoms/cm³. If a lead concentration is 1×10¹⁵atoms/cm³ or less, lead elements are localized and thus the catalyticfunction of lead is deteriorated. Further, if a lead concentration is5×10¹⁹ atoms/cm³ or more, lead and silicon are reacted with each otherto form lead-silicon compounds, and the semiconductor characteristicsare hindered. In a crystallized state, products can be more practicallyused as a semiconductor as the lead concentration is lower.

On the basis of the above consideration and the fact that products areused as active layers or the like of TFTs, the lead addition amount isrequired to be adjusted in the range of 1×10¹⁵ atoms/cm³ to 1×10¹⁹atoms/cm³.

As explained below, in the case that lead is not added, crystallizationoccurs from crystal nuclei existing at the substrate surface. Thiscrystallization proceeds in a random direction provided that the film isnot thicker than a certain thickness. Further, if the thickness of thefilm is enough large, the columnar crystals grow in such a manner thatthe (110) direction aligns vertically to the substrate surface. Thiscrystallization can be observed on the entire surface of the substrate.On the other hand, in the case of the trace lead addition according tothis embodiment, different crystal growth was observed between an areaadded with lead (hereinafter referred to as "lead area") and an area inthe neighborhood of the lead area (hereinafter referred to as "adjacentarea"). That is, it became clear from a transmission electronmicroscopic photograph that, in the lead area, added lead or a compoundof lead and silicon served as a crystal nucleus and the pillar-shapedcrystal growth progressed substantially vertically to the substrate. Inaddition, the low-temperature crystallization was also confirmed in theadjacent area in which the lead was not directly added, and a peculiarcrystal growth in which needle or pillar shape crystals grewsubstantially in parallel to the substrate so that the (111) plane wasaligned vertically to the substrate was also observed in this area.

It was observed that the crystal growth in the lateral directionparallel to the substrate was started from the lead area and the maximumcrystal size of grown crystals extended to several hundreds μm, and itbecame clear that the degree of crystal grow increases with the increaseof the time and the temperature. For example, crystal growth of about 40μm crystals was observed at the temperature of 550° C. and for 4 hours.In addition, according to a transmission electron microscopicphotograph, each of these large-size laterally-extending crystals wasdetermined to be like monocrystal. Further, the lead concentration ineach of a trace lead added area, a laterally-extending crystal growtharea in the neighborhood of the trace lead added area and an amorphousarea (no low-temperature crystallization appeared in a region extremelydistant from the Pd added area) was measured by SIMS (Secondary Ion MassSpectroscopy). As a result, the lead concentration in thelaterally-extending crystal growth area was measured to be lower thanthe trace lead added area by one figure, and diffusion in amorphoussilicon was observed. Further, the lead concentration in the amorphousarea was measured to be lower than the laterally-extending crystalgrowth area by one figure. The relationship between the crystal form andthe above result has been unclear at present, however, at any rate, asilicon film having crystallinity of a desired crystal form at a desiredarea can be formed by adjusting a lead addition amount and controlling aposition where lead is added.

Next, electrical characteristics of the trace lead added area and thelaterally-extending crystal growth area adjacent thereto will bedescribed.

With respect to conductivity, the trace lead added area had thesubstantially same conductivity value as a no-lead added film, that is,the film which was subjected to crystallization at about 600° C. forseveral tens hours. Further, calculating an activation energy on thebasis of temperature-dependence of conductivity, there was observed nobehavior which was expected to be induced due to the lead energy levelwhen the lead addition amount was set in the range of about 10¹⁷atoms/cm³ to 10¹⁸ atoms/cm³. That is, according to only this fact, in acase where the lead concentration in a crystal silicon semiconductorfilm is below 1×10¹⁸ atoms/cm³, there would occur no problem even if asemiconductor device, for example, a TFT is formed using this film.

On the other hand, the laterally-extending crystal growth area had ahigher conductivity than the trace lead added area by one or morefigures, and it has a very higher value as a silicon semiconductorhaving crystallinity. The reason for this fact would be considered asfollows. That is, a current passing direction was coincident with thelaterally-growing direction of crystals, and thus there was little or nograin boundary in an electron path between electrodes. This fact isperfectly consistent with the result of the transmission electronmicroscopic photograph.

However, through more delicate observation of the laterally-growing areaof the crystals on the transmission electron microscopic photograph,areas containing crystals growing in a branch form was also observedupon viewing from the upper side of the substrate although thecrystallization direction of needle or pillar crystals was parallel tothe surface of the substrate. That is, it was observed that the needleor pillar crystals grew in the same direction on the average, however,some crystals grew while being branched in a slant direction.

The inventors have deliberately considered the observation result, andhad the following conclusion.

Crystal components of a substrate material existing in a substrate or atan interface portion between the substrate and a semiconductor film, orcrystal components in the semiconductor film can serve as nuclei forcrystal growth, however, these components obstruct the crystal growth inan uniform direction (unidirection) and promote a random crystal growthin the lateral crystal growth process.

Therefore, this invention is characterized in that crystal components atand in the vicinity of the interface between a substrate area on whichthe growth is to occur and an amorphous silicon semiconductor film (inthis invention, the term "amorphous" does not mean a perfect amorphousstate, but may contain crystal components if the amount of thecomponents is small) are removed to the utmost by an ion implantation ofinert elements so that this area is made perfectly amorphous, and thenby performing the crystal growth in a lateral direction (a directionparallel to the substrate) in a state where no component serving as acrystal nucleus exists, needle or pillar crystals are grown so that thecrystal growing directions thereof are coincident with one another as awhole. Particularly by concentratively implanting inert ions into thesubstrate, the area in the neighborhood of the surface of the substrate(when a blocking film is formed on the surface of the substrate, theblocking film is regarded as the substrate surface), the interfacebetween the substrate and the semiconductor film and the semiconductorfilm itself are made perfectly amorphous, so that components havingcrystallinity which might serve as crystal nuclei are removed asperfectly as possible.

In accordance with another aspect of the invention, it is possible tofurther improve the characteristics of the thus obtained semiconductorlayer by further treating the semiconductor layer with a laser light oran intense light such as a flush lamp as strong as the laser light.Thereby, components existing at grain boundaries or the like and nothaving been sufficiently crystallized can be further crystallized. It isassumed that the crystalline components which are produced by thepreceding heating step function as nuclei so that the remainingamorphous components can be further crystallized by the photo-annealing.

The invention and its application to the actual semiconductor deviceswill be more fully understood from the following detailed description,when taken with the appended drawings, in which:

BRIEF DESCRIPTION OF THE DRAWINGS

FIGS. 1A to 1D are cross-sectional views showing a series of processesof a semiconductor device producing method according to a firstembodiment of this invention;

FIG. 2 is a top view of a semiconductor device as shown in FIG. 1D,which is formed by the semiconductor device producing method accordingto the first embodiment of this invention;

FIGS. 3A to 3D are cross-sectional views showing a series of processesof a semiconductor device producing method according to a secondembodiment of this invention;

FIG. 4 is top view of a TFT which is formed by the semiconductor deviceproducing method according to the second embodiment of this invention;

FIG. 5 is a graph showing dose of silicon ions;

FIG. 6A to 6E are cross-sectional views showing a manufacturing processof a semiconductor device in accordance with a fourth embodiment of theinvention; and

FIGS. 7A and 7B are TEM photographs of the semiconductor layer obtainedin the fourth embodiment of the invention.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS

[First Embodiment]

This embodiment relates to a method of forming a complementary circuitcomprising a P-channel type TFT (PTFT) and a N-channel type TFT (NTFT)which are formed of crystal silicon on a glass substrate, and arecomplementarily connected to each other. The scheme of this embodimentis applicable to, for example, a peripheral driver circuit for an activetype of liquid crystal display device or an image sensor.

FIGS. 1A to 1D are cross-sectional views showing a series of processesto manufacture a semiconductor device according to a first embodiment ofthis invention.

A blocking film 102 of silicon oxide is first formed at a thickness of2000 Å on a substrate 101 (coring 7059) by a sputtering method, and thena silicon oxide film 103 serving as a mask is provided on the blockingfilm 102. The silicon oxide film 103 is used to expose the blocking film102 in a slit form, and it must be designed at a thickness of 1000 Å ormore. Further, it is effective to add the mask 103 with a materialhaving a gettering effect such as phosphorus, chlorine or the like.Viewing this structure from the upper side as shown in FIG. 1A, theblocking film 102 is exposed to the outside in a slit form at region100, and the other portion is masked.

After the silicon oxide film 103 is formed, a lead film is selectivelyformed at a thickness of 5 to 200 Å, for example, 20 Å in the area 100by a sputtering method. That is, the trace lead addition is selectivelyperformed on the silicon oxide 102 in the area 100.

Thereafter, the silicon oxide film 103 serving as the mask is removed,and an intrinsic (I-type) amorphous silicon film 104 is formed at athickness of 500 to 1500 Å, for example, 1000 Å. A film havingcrystallinity may be used as the amorphous silicon film 104, that is,any film may be used insofar as it is a non-single crystalline siliconfilm. Further, a silicon oxide film 99 serving as a protective film isformed at a thickness of 100 to 1000 Å. The silicon oxide film isprovided to prevent the surface of the silicon film 104 from beingdamaged when a subsequent ion implantation is performed.

Thereafter, silicon ions which are inert elements to the silicon film104 are implanted to the whole surface. The implantation of the siliconions is performed to remove crystal components (silicon oxide crystalcomponents in the substrate and crystal components in the amorphoussemiconductor film) which exist at the interface between the substrate(containing the blocking film 102) and the amorphous siliconsemiconductor film so that the crystal growth in the uniform directioncan be performed in a subsequent heat-annealing process.

Implantation conditions are set so that the silicon ions are implantedat a dose configuration as shown in FIG. 5. In FIG. 5, an arearepresented by a dotted line corresponds to an interface portion betweenthe blocking film 102 and the amorphous silicon film 104. The maximumvalue of the dose was set to 5×10¹⁴ cm⁻² at the substrate side. That is,the acceleration voltage is controlled so that the peak of theconcentration locates under the silicon semiconductor layer. In thesilicon-ion implantation process, the interface between the blockingfilm 102 (in this embodiment, the blocking film 102 is regarded asconstituting the surface of the substrate) and the amorphous siliconfilm 104, the amorphous silicon film 104 itself, the interface betweenthe amorphous silicon film 104 and the silicon oxide film 99, and asurrounding portion to the interface are made amorphous. The dose of thesilicon ions is preferably in the range of 1×10¹⁴ to 9×10¹⁶ cm⁻². Also,the accelerating voltage is 137 keV, for example.

Since the surface of the amorphous silicon film is coated with thesilicon oxide film 99 during the silicon-ion implantation, damage of theamorphous silicon film by accelerated ions can be suppressed. Further,it is preferable to provide a mask on the region 100 in order to preventthe implantation of the silicon ions into this area. Thereby, it ispossible to prevent undesirable diffusion of lead into other portions ofthe film during the implantation of silicon ions.

Thereafter, the silicon oxide film 99 is removed, and an annealingtreatment is conducted at 550° C. for 4 hours under a hydrogen reducingatmosphere (preferaby, partial pressure of hydrogen is set to 0.1 to 1atm) or a nitrogen atmosphere (atmospheric pressure) to crystallize theamorphous silicon film 104. In this case, the silicon film 104 iscrystallized in a direction vertical to the substrate 101 in the area100 where the lead film has been selectively formed. In areas other thanthe area 100, the crystal growth proceeds in a lateral direction (adirection parallel to the substrate) from the area 100. Thecrystallization temperature may be set in the range of 450° C. to 700°C. If the crystallization temperature is too high, a problem in heatresistance of the glass substrate occurs like the prior art. In thepresent invention, it is possible to crystallize the film at a lowertemperature than the conventional process at 600° C., that is, at 500°C.-580° C., preferably, 520° C.-560° C.

Since the interface between the blocking film 102 and the silicon film104, the peripheral portion thereof and the amorphous silicon filmitself are perfectly made amorphous in the laterally crystal-growingarea, there occurs no crystal component serving as an element ofdisturbing a crystallization direction as shown by an arrow 105 whencrystallization occurs, so that the lateral crystal growth can beuniformly performed.

Through the above process, the amorphous silicon film can becrystallized to obtain the crystal silicon film 104. Thereafter, apatterning process is performed to separate elements from one another,and the silicon oxide film 106 is formed at a thickness of 1000 Å as agate insulating film by the sputtering method. In the sputteringprocess, silicon oxide is use as a target, and the following sputteringconditions are adopted: a substrate temperature of 200 to 400° C., forexample, 350° C., and a sputtering atmosphere of oxygen and argon(argon/oxygen=0 to 0.5, for example, below 0.1). Subsequently, analuminum film (containing silicon of 0.1 to 2%) is formed at a thicknessof 6000 to 8000 Å, for example 6000 Å, by the sputtering method. It ispreferable to successively carry out the film forming processes of thesilicon oxide film 106 and the aluminum film.

Thereafter, the aluminum film is subjected to the patterning to formgate electrodes 107 and 109. Further, the surfaces of the aluminumelectrodes are subjected to anodic oxidation to form oxide layers 108and 110 on the surfaces thereof. The anodic oxidation is performed in anethylene glycol solution containing tartaric acid of 1 to 5%. The oxidelayers 108 and 110 thus obtained have a thickness of 2000 Å. Thethickness of the oxide layers 108 and 110 serves to determine an offsetgate area in a subsequent ion doping process, and thus the length of theoffset gate area can be determined in the anodic oxidation process asdescribed above.

Thereafter, impurities (phosphorus and boron) are doped into the crystalsilicon film area using the gate electrode 107 and its peripheral oxidelayer 108, and the gate electrode 109 and its peripheral oxide layer 110as a mask by the ion doping method. Phosphine (PH₃) and diborane (B₂ H₆)are used as doping gas. In the former case, an accelerating voltage isset to 60 to 90 kV, for example, 80 kV, and in the latter case theaccelerating voltage is set to 40 to 80 kV, for example, 65 kV. The doseis set to 1×10¹⁵ to 8×10¹⁵ cm⁻², for example, it is set to 2×10¹⁵ cm⁻²for phosphorus and 5×10¹⁵ cm⁻² for boron. In the doping process, each ofthese elements is selectively doped into the corresponding area whileshielding the other area by a photoresist. As a result, N-type impurityareas 114 and 116 and P-type impurity areas 111 and 113 are formed, andthus a P-channel type TFT (PTFT) area and an N-channel type TFT (NTFT)area can be formed.

Thereafter, an annealing process is performed by irradiation of laserbeam. A KrF excimer laser (wavelength: 248 nm, pulse width:20 nsec) areused, however, other lasers may be used. The following irradiationconditions of laser beam are used: energy density of 200 to 400 mJ/cm²,for example, 250 mJ/cm², and 2 to 10 shots, for example, 2 shots per onepoint. Further, it is effective to heat the substrate at about 200 to450° C. in the laser beam irradiating operation. In the laser annealingprocess as described above, the irradiation of the laser beam morepromotes recrystallization because lead has been diffused into thepreviously-crystallized area, and thus the impurity areas 111 and 113which are doped with the impurities providing P-type conductivity andthe impurity areas 114 and 116 which are doped with the impuritiesproviding N-type conductivity can be easily activated.

Subsequently, a silicon oxide film 118 having 6000 Å thickness is formedas an interlayer insulator by a plasma CVD method, contact holes areformed in the silicon oxide film 118, and then electrodes/wirings 117,120 and 119 are formed of conductive material, for example, amulti-layer film of titanium nitride and aluminum. Finally, an annealingprocess is performed at 350° C. for 30 minutes under a hydrogenatmosphere of 1 atm. A semiconductor circuit is completed in a series ofprocesses as described above (FIG. 1D).

The circuit shown in FIG. 1D includes a CMOS structure in which the PTFTand the NTFT are complementarily formed, however, in the aboveprocesses, two independent TFTs may be simultaneously formed by formingtwo TFTs simultaneously and cutting and separating these TFTs at thecenter thereof.

FIG. 2 is a top view of the semiconductor device shown in FIG. 1D. ThePd-added area in FIG. 2 corresponds to the area 100 shown in FIG. 1A.The lateral crystallization is started from the Pd-added area andprogresses substantially uniformly in parallel to the substrate as shownin FIG. 2. Since needle or pillar shaped crystals grow in a movingdirection of carriers which move between a source and a drain, thecarriers hardly traverse grain boundaries, and thus TFTs having highmobility can be obtained.

For example, when crystallization was performed without implantation ofsilicon ions in the process of FIG. 1B, the mobility of an obtained PTFTwas 50 to 60 cm² /Vs. On the other hand, the mobility of a PTFT obtainedin this embodiment was 90 to 120 cm² /Vs. Further, an NTFT obtainedwithout silicon-ion implantation had a mobility of 80 to 100 cm² /Vs,however, an NTFT obtained in this embodiment had a mobility of 150 to180 cm² /Vs.

In this embodiment, as a Pd doping method, the Pd thin film (as it isextremely thin, it is difficult to observe it as a film) is selectivelyformed on the blocking film 102 below the amorphous silicon film 104,and the crystal growth is started from this portion. However, it may beadopted that the amorphous silicon film 104 is formed and then the leadfilm is selectively formed. That is, the crystal growth may be startedfrom the upper surface of the amorphous silicon film, or from the lowersurface of the amorphous silicon film. Further, it may be adopted thatan amorphous silicon film is beforehand formed, and lead ions areselectively doped into the amorphous silicon film 104 by the ion dopingmethod. In this case, the concentration of Pd can be controlled.Further, the trace Pd addition can be performed by a plasma treatment.When lead element is doped using the plasma treatment, it is sufficientto conduct the plasma treatment on the upper surface of a blocking film(silicon oxide film 102, for example) of a semiconductor film (amorphoussilicon film 104, for example) which is to be subjected to the tracelead addition, or on the upper surface of the semiconductor film.

Further, TFTs can be manufactured in the same process when other groupIV elements such as Sn is used as catalytic material for crystallizationin place of Pd.

[Embodiment 2]

In this embodiment, an N-channel type TFT is provided to each pictureelement as a switching element in an active-type liquid crystal displaydevice. In the following description, the structure is described for onepicture element, however, other many (generally, several hundredthousands) picture elements can be made by the similar process.

FIGS. 3A to 3D are cross-sectional views showing a series of producingprocesses of a semiconductor device according to this embodiment. Inthis embodiment, a Corning 7059 glass substrate is used as a substrate201. First, a blocking film 202 (silicon oxide film) is formed on theglass substrate 201 by the sputtering method, and then a silicon oxidefilm 203 serving as a mask is formed at a thickness of 1000 Å. Thesilicon oxide film serves as a mask for exposing the blocking film 202to the outside in an area 204. Thereafter, a lead film is formed. (notshown in the figure) The lead film is formed at a thickness of 5 to 200Å, for example, 20 Å by the sputtering method, and its chemical formulais represented by NiSi_(x), 0.4≦×≦2.5, for example, ×=2.0.

Thereafter, the silicon oxide film 203 serving as the mask is removed,an amorphous silicon film 205 (thickness: 300 to 1500 Å) is formed by anLPCVD method or a plasma CVD method, and then a protection film 200 ofsilicon oxide is formed at a thickness of 500 Å A (FIG. 3B).

Subsequently, the same silicon-ion implantation process as the firstembodiment is performed, and then the crystallization is performed bythe heat-annealing treatment. This annealing process is performed at550° C. for 4 hours under a hydrogen-reducing atmosphere (preferably, apartial pressure of hydrogen is 0.1 to 1 atom). In this case, since alead film is partially formed below the amorphous silicon film 205, thecrystal growth at a portion where the lead film is formed progresses ina vertical direction to the substrate, and the crystal growth at theother portions progresses in parallel to the substrate to obtain acrystal silicon film.

The silicon semiconductor layer 205 thus crystallized is patterned sothat a semiconductor island including an active region of a TFT isformed as shown in FIG. 3B. Then a gate insulating film 206 of siliconoxide (at a thickness of 700 to 1200 Å, for example, 1000 Å in thisembodiment) is formed by a plasma CVD method using tetra-ethoxy-silane(TEOS) as row material under an oxygen atmosphere.

Subsequently, a gate electrode 207 of silicon is formed, and thenphosphorus is doped as N-type impurities into the crystal silicon filmin a self-alignment manner by the ion doping method to form source anddrain regions 208 and 210 of the TFT. Further, as shown in an arrow ofFIG. 3C, KrF laser beam is irradiated to the above crystal silicon film,thereby improving crystallinity of the silicon film which isdeteriorated due to the ion doping process as described above. At thistime, the energy density of the laser beam is set to 250 to 300 mJ/cm².By the laser irradiation as described above, the sheet resistance of thesource and drain regions of the TFT is set to 300 to 800 Ω/cm².

Thereafter, an insulating layer 211 are formed with silicon oxide, and apixel electrode 212 are formed with ITO. Subsequently, contact holes areformed in the insulating layer 211, and electrodes 213 and 214 areformed with a multi-layer film. of chromium/aluminum at the source anddrain regions of the TFT so that the electrode 214 is connectedly theITO. The chromium/aluminum multi-layer film comprises a chromium filmserving as a lower layer which has a thickness of 100 to 2000 nm,typically 100 nm, and an aluminum film serving as an upper layer whichhas a thickness of 100 to 2000 nm, typically 500 nm. It is preferable tocontinuously form these films by the sputtering method. Finally, theannealing treatment is conducted at 200 to 300° C. for 2 hours in ahydrogen atmosphere to complete hydrogenation of silicon. In the manneras described above, the TFT is completed. A number of TFTs which aresimultaneously formed in the manner as described above are arranged in amatrix form to form an active matrix type of liquid crystal displaydevice.

FIG. 4 is a top view of the TFT which is formed by the producing methodof this embodiment.

In FIG. 4, there are shown a TFT portion, an area 204 which is subjectedto the trace lead addition, source/drain regions 208 and 210, a channelforming region 209, and a gate electrode 209 above the channel formingregion. In a crystallization process using the heat-annealing treatment,the crystal growth having a uniform crystal growing direction progressesfrom the area 204 in which lead is selectively introduced, in parallelto the substrate as indicated by an arrow of FIG. 4, and thesource/drain regions 208 and 210 and the channel forming region 209 areconstructed with a crystal silicon film which grows in parallel to thesubstrate. At an operation time of the TFT, carriers move along thechannel forming region, that is, between the regions 208 and 210, sothat the carriers can be moved in the crystal silicon film whose crystalgrowing direction is uniform, with suffering no effect of grainboundaries, that is, a high mobility can be obtained. Further, thelateral crystal growth progresses by about 40 μm, and thus it ispreferable to set the length of an active layer to 40 μm or less. Inaddition, the area added with a very small amount of lead (trace leadadded area) may be overlapped with the drain/source region 210. However,if the channel forming area 209 is overlapped with the trace lead addedarea 204, the crystal growing direction would be vertical to thesubstrate, and thus attention must be paid to this point.

In the embodiment as described above, the TFT is formed so that thecarriers flow in parallel to the crystal growing direction, however, thecharacteristics of the TFT can be freely controlled by suitablydetermining the flow direction of the carriers in the TFT and thecrystal growing direction. That is, a rate at which the carrierstraverse grain boundaries can be controlled by adjusting an intersectingangle between the carrier flow direction (a direction connecting thesource and the drain) and the crystal growing direction in the TFT, sothat resistance against movement of the carriers can be controlled tosome degree.

[Embodiment 3]

In this embodiment, the ion doping of silicon ions is selectivelyperformed so that an area where no silicon ion is doped is selectivelyleft as a silicon film having crystal components, thereby enabling thelateral crystal growth to progress from this area toward an amorphousarea where silicon ions are doped.

For example, in the producing process shown in FIG. 1, the trace leadaddition is selectively conducted on the area 100 like the embodiment 1,and in the producing process shown in FIG. 1B, the area 100 is masked bya resist to perform the ion doping of silicon ions. In this case, it isbetter to form the silicon film 104 as a film having crystallinity. Inthis case, the crystal growth as indicated by the arrow 105 occurs fromthe region 100 of the silicon film 104 toward its peripheral portion(the area doped with no silicon ion) when the heat-crystallization isperformed.

Further, the same effect can be obtained by performing the trace leadaddition for the whole silicon film 104. In this case, the crystalgrowth in the vertical direction to the substrate 101 simultaneouslyoccurs while lead acts as a catalyst.

[EMBODIMENT 4]

FIGS. 6A to 6E show cross-sectional views of the manufacturing processof a pair of thin film transistors in accordance with the fourthembodiment of the invention. A silicon oxide layer 602 is formed on aglass substrate 601 to a thickness of 1000-5000 Å, for example 2000 Å.Then, an amorphous silicon layer 603 is formed through a conventionalplasma CVD to a thickness of 500-1500 Å, for example, 500 Å. And then, asilicon oxide layer 604 is further formed on the amorphous silicon layer603 to a thickness of 500-1500 Å, for example 500 Å. It is desirable toform these films successively. As shown in FIG. 6A, an opening 605 isformed in the silicon oxide layer 604 by selectively etching the layer604 in order to introduce lead in the later step. The opening 605 islocated in such a manner that it does not overlap channel regions of theTFTs to be formed within the silicon layer 603.

After forming the opening, a layer 607 containing a lead salt is formedon the above structure by a spin-coating method as explained below.

Initially, lead acetate or lead nitrate is diluted with water or ethanolso that the concentration is controlled to be 25-200 ppm, for example100 ppm. On the other hand, the substrate is immersed into a hydrogenperoxide or a mixture of hydrogen peroxide and ammonium to form anextremely thin silicon oxide layer on the exposed portion of theamorphous silicon film (in the opening 605). This will improve theinterfacial affinity between the lead solvent and the amorphous siliconlayer.

Then, the substrate is placed on a spin coater and slowly rotated. Theabove obtained lead solvent is dropped onto the rotating substrate at1-10 ml, for example, 2 ml in order to spread the solvent on the entiresurface of the substrate. This condition is maintained for 1-10 minutes,for example, 5 minutes. Subsequently, the rotation speed of thesubstrate is increased and a spin dry is performed. These steps may beperformed repeatedly. Thus, a thin film 607 of a lead salt is obtainedas shown in FIG. 6A.

Next, an implantation of silicon ions is performed by an ionimplantation method. At this time, the implantation is performed in sucha manner that the concentration of the silicon ions is maximum at theboundary between the underlying silicon oxide layer 602 and theamorphous silicon layer 603 in the region covered with the silicon oxide604. In the region under the opening 605, the silicon ions are moredeeply implanted.

Then, the substrate is heated in a furnace at 520-580° C., for example550° C. and for 4-12 hours, for example 8 hours. The surroundingatmosphere is nitrogen. As a result, the lead initially diffuses intothe region of the amorphous silicon under the opening 605 and acrystallization starts there. Further, the crystallization spreads toits surrounding portion as shown by arrows in FIG. 6B.

Then, in order to improve the crystallinity of the silicon layer, thelayer is irradiated with KrF excimer laser (wavelength: 248 nm) or XeClexcimer laser (wavelength: 308 nm) at 1-20 shots, for example, 5 shotsin air or oxygen atmosphere. (FIG. 6C)

Then, the silicon layer 603 is etched to form TFT regions. A siliconoxide layer 609 is formed on the entire surface to a thickness of1000-1500 Å, for example, 1200 Å. Also, in the same manner as inEmbodiment 1, a gate electrode 610 for a PTFT and a gate electrode 613for an NTFT made of aluminum, an anoxic oxidation film 612, 614 areformed to obtain a gate portion of the TFT.

Then, an n-type impurity and a p-type impurity are respectivelyintroduced into the semiconductor layer by using the gate portion as amask. As a result, source 615, channel 616, drain 617 of the PTFT andsource 620, channel 619 and a drain 618 of the NTF for a peripheralcircuit are formed. Subsequently, a laser irradiation is performed onthe entire surface of the structure in order to activate the dopedimpurity in the same manner as in the first embodiment. (FIG. 6D).

Finally, a silicon oxide layer 621 is formed to a thickness of 3000-8000Å, for example, 5000 Å as an interlayer insulating film, following whichcontact holes are opened for source and drain regions of the TFTs, and adouble-layer of titanium nitride (1000 Å thick) and aluminum (5000 Å)are deposited by sputtering to form electrode/wirings 622-644. In themanner described above, an invertor circuit of a PTFT and an NTFTcomprising a crystalline silicon in which the crystal growth occurred ina lateral direction. (FIG. 6E)

As explained above in conjunction with FIG. 6C, since a laserirradiation is performed in this embodiment, the amorphous componentsremaining in a space between the needle-like crystals can be furthercrystallized. Moreover, this crystallization proceeds in such a mannerthat a cross-sectional area of the needle-like crystals become larger.This means that the region in which electrical current is to be passedis expanded and thus a more large drain current can be obtained.

The above condition is shown in FIGS. 7A and 7B which are photographs ofthe silicon crystals observed with a transmission type electronmicroscopy (TEM). In FIG. 7A, top ends of the needle-like crystals areseen. As can been seen, the crystals grew in a lateral direction andalso, there are number of amorphous regions between the crystals. Thiscondition is observed after the heat crystallization.

FIG. 7B shows the condition when the foregoing semiconductor layer wasfurther irradiated with a laser light in accordance with the presentinvention. It is observed that the amorphous region which occupies themost area of the semiconductor layer was crystallized. Most of thiscrystallization was randomly proceeded and an electrical property is notso good. However, it should be noted that the amorphous regionintervening between the crystals as shown in FIG. 7A was crystallizedbased on the already formed needle-like crystals. Accordingly, a morelarge crystalline region in which the crystalline orientation issubstantially uniform can be obtained by the subsequent laserirradiation.

FIGS. 7A and 7B are directed to the top ends of the crystals where thereare observed relatively a lot of amorphous regions for the purpose ofeasier understanding of the above phenomena. However, the same appliesto the bottom portion or a middle portion of the crystals.

According to this invention, by selectively introducing metal elementpromoting crystallization into a specific area and starting crystalgrowth from this area in a lateral direction (in parallel to asubstrate), a crystal silicon film having uniform crystal growthdirection can be obtained. In this case, in order to beforehandextinguish crystal components at an area where the lateral crystalgrowth progresses, this area is doped with inert ions to be perfectlymade amorphous, and then subjected to a heat-annealing treatment toobtain a crystal semiconductor film having uniform crystal growthdirection. If TFTs are manufactured using the film thus formed, highmobility can be provided to the TFTs.

Further, in accordance with another aspect of the invention, the laserirradiation subsequent to the heat crystallization reduces the amorphousregion and make the crystals in the shape of a needle more larger. Thus,the characteristics of TFTs can be improved.

In the preferred embodiments of the invention, lead is used as acrystallization promoting agent. However, the invention should not belimited to the use of the lead, rather, other materials may be replacedfor lead, for example, Ni, Fe, Pt, Co, and Pd.

While this invention has been described above in connection with variouspreferred and alternative embodiments, it is understood that persons ofordinary skill in the art can make numerous modifications withoutdeparting from the scope of the invention as claimed in the appendedclaims.

What is claimed is:
 1. A semiconductor device comprising:a crystallinesemiconductor film comprising silicon formed over an insulating surface,said crystalline semiconductor film being an active layer of a thin filmtransistor having at least one of channel, source, drain regions andcontaining a catalyst for promoting crystallization of silicon, whereinsaid catalyst is selected from group IV elements, wherein said channelregion contains said catalyst at a concentration of 1×10¹⁵ -5×10¹⁹atoms/cm³, and wherein said channel region comprises a plurality ofcrystals extending in a direction connecting said source and drainregions.
 2. A device according to claim 1, wherein said catalyst isselected from the group IV elements consisting of Sn and Pb.
 3. A deviceaccording to claim 1, wherein said catalyst concentration contained insaid channel region is measured by Secondary Ion Mass Spectroscopy.
 4. Adevice according to claim 1, wherein said semiconductor film ispolycrystalline.
 5. A semiconductor device comprising:a crystallinesemiconductor film comprising silicon formed over an insulating surface,said crystalline semiconductor film being an active layer of a thin filmtransistor having at least one of channel, source, drain regions andcontaining a catalyst for promoting crystallization of silicon, whereinsaid catalyst is selected from group IV elements, wherein said channelregion comprises a plurality of crystals extending substantially inparallel to said insulating surface and in a direction connecting saidsource and drain regions, and wherein said channel region contains saidcatalyst at a concentration of 1×10¹⁵ -5×10¹⁹ atoms/cm³.
 6. A deviceaccording to claim 5, wherein said catalyst is selected from the groupIV elements consisting of Sn and Pb.
 7. A device according to claim 5,wherein said catalyst concentration contained in said channel region ismeasured by Secondary Ion Mass Spectroscopy.
 8. A device according toclaim 5, wherein said semiconductor film is polycrystalline.
 9. A deviceaccording to claim 5, wherein said plurality of crystals extend in auniform direction.
 10. A semiconductor device comprising:a crystallinesemiconductor film comprising silicon formed over an insulating surface,said crystalline semiconductor film being an active layer of a thin filmtransistor having at least one of channel, source, drain regions andcontaining a catalyst for promoting crystallization of silicon, whereinsaid catalyst is selected from group IV elements, and wherein saidchannel region comprises a plurality of crystals extending the samedirection and contains said catalyst at a concentration of 5×10¹⁹atoms/cm³ or less, and wherein an intersecting angle between saidcrystals extending direction and a direction connecting source and drainregions is adjusted in order to control resistance against movement ofcarriers in the channel region.
 11. A device according to claim 10,wherein said catalyst is selected from the group IV elements consistingof Sn and Pb.
 12. A device according to claim 10, wherein said catalystconcentration contained in said channel region is measured by SecondaryIon Mass Spectroscopy.
 13. A device according to claim 10, wherein saidsemiconductor film is polycrystalline.
 14. A semiconductor devicecomprising:a crystalline semiconductor film comprising silicon formedover an insulating surface, said crystalline semiconductor film being anactive layer of a thin film transistor having at least one of channel,source, drain regions and containing a catalyst for promotingcrystallization of silicon, wherein said catalyst is selected from groupIV elements, and wherein said channel region comprises a plurality ofcrystals extending substantially in parallel to said insulating surface,wherein said channel region contains said catalyst at a concentration of5×10¹⁹ atoms/cm³ or less, wherein an intersecting angle between saidcrystals extending direction and a direction connecting source and drainregions is adjusted in order to control a rate at which carrierstraverse grain boundaries in the channel region.
 15. A device accordingto claim 14, wherein said catalyst is selected from the group IVelements consisting of Sn and Pb.
 16. A device according to claim 14,wherein said catalyst concentration contained in said channel region ismeasured by Secondary Ion Mass Spectroscopy.
 17. A device according toclaim 14, wherein said semiconductor film is polycrystalline.
 18. Adevice according to claim 14, wherein said plurality of crystals extendin a uniform direction.
 19. A device according to claim 1, wherein saidsemiconductor device comprising at least one thin film transistor formedover a substrate having said insulating surface.
 20. A device accordingto claim 1, wherein said semiconductor device is an active matrix typedisplay device or an image sensor.
 21. A device according to claim 5,wherein said semiconductor device comprising at least one thin filmtransistor formed over a substrate having said insulating surface.
 22. Adevice according to claim 5, wherein said semiconductor device is anactive matrix type display device or an image sensor.
 23. A deviceaccording to claim 10, wherein said semiconductor device comprising atleast one thin film transistor formed over a substrate having saidinsulating surface.
 24. A device according to claim 10, wherein saidsemiconductor device is an active matrix type display device or an imagesensor.
 25. A device according to claim 14, wherein said semiconductordevice comprising at least one thin film transistor formed over asubstrate having said insulating surface.
 26. A device according toclaim 14, wherein said semiconductor device is an active matrix typedisplay device or an image sensor.